화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.122, No.11, 2556-2566, 2000
Solid-state Nb-93 NMR and Nb-93 nutation studies of polycrystalline Pb(Mg1/3Nb2/3)O-3 and (1-x)Pb(Mg1/3Nb2/3)O-3/xPbTiO(3) solid-solution relaxor ferroelectrics
Solid-state Nb-93 static and MAS NMR and Nb-93 nutation studies of polycrystalline Pb(Mg1/3Nb2/3)O-3, (PMN) and (1 -x)Pb(Mg1/3Nb2/3)O-3/xPbTiO(3) (x = 0.05 to 0.50) solid-solutions are reported. The Nb-93 static and MAS NMR spectra of PMN measured at 14.1 T have two major resonances due to the central transition (1/2 <-> -1/2), a sharp peak at -902 ppm (1950 Hz fwhh) and a broad resonance (12 800 Hz fwhh) centered at -980 ppm. Two-dimensional Nb-93 nutation spectra measured at 9.4 T, by contrast, have three different resonances, a sharp peak due to niobiums with a C-Q < 0.8 MHz that is correlated with the sharp Nb-93 signal at -902 ppm, and two resonances due to niobiums with a C-Q of approximate to 17 MHz and a C-Q > 62 MHz, respectively, that are associated with the broad Nb-93 peak centered at -980 ppm. The sharp Nb-93 peak for PMN is assigned to Nb(V) B-sites of cubic or high local symmetry in Mg(II)-rich regions with Nb(OMg)(6) configurations. The broad Nb-93 resonance at -980 ppm is assigned to a range of Nb(ONb)(6-x)(OMg)(x) site configurations, where x = 0 to 5, contained in the Nb(V)-rich regions in PMN. The lower symmetry of these Nb(V) B-sites is likely due to neighboring Mg/Nb B-site distributions, that alter the Nb-O bond lengths and O-Nb-O bond angles. Substantially different 93Nb NMR and nutation behavior is observed for(1 - x)PMN/xPT powders (x = 0.05 to 0.50). Decreased intensity of the sharp -902 ppm peak is due to increasing incorporation of Ti4+ ion from PT into the B-sites of Nb(OMg)(6) configurations in 5 to 50 mol % PMN/PT solid-solutions. Increasing substitution of Ti4+ ions into the Nb(V) B-sites of Nb(ONb)(6-x)(OMg)(x) configurations at higher mol % PT (similar to 34 to 50 mol % PT) is also correlated with line shape changes of the broad Nb-93 MIR peak at -980 ppm and changes in the shape of the contour plots of the nutation spectra. In addition, chemical shift and quadrupolar dispersion effects likely contribute to the observed line shape of the -980 ppm peak for the 0.50PMN/0.50PT sample as a result of B-site occupation by three different cations (Mg2+, Ti4+, and Nb5+) in the different Mg(II)- and Nb(V)-rich substructural regions in PMN/PT materials.